EP0971230A1 - Bestimmung der Biodegradabilität von Iminodiessigsäurederivateb, abbaubare Chelatbildner sowie deren Verwendung und Zusammensetzungen damit - Google Patents

Bestimmung der Biodegradabilität von Iminodiessigsäurederivateb, abbaubare Chelatbildner sowie deren Verwendung und Zusammensetzungen damit Download PDF

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EP0971230A1
EP0971230A1 EP99115513A EP99115513A EP0971230A1 EP 0971230 A1 EP0971230 A1 EP 0971230A1 EP 99115513 A EP99115513 A EP 99115513A EP 99115513 A EP99115513 A EP 99115513A EP 0971230 A1 EP0971230 A1 EP 0971230A1
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distance
formula
chelate
compounds
chelants
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Alan D. Strickland
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Dow Chemical Co
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Dow Chemical Co
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16B—BIOINFORMATICS, i.e. INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR GENETIC OR PROTEIN-RELATED DATA PROCESSING IN COMPUTATIONAL MOLECULAR BIOLOGY
    • G16B15/00—ICT specially adapted for analysing two-dimensional or three-dimensional molecular structures, e.g. structural or functional relations or structure alignment

Definitions

  • This invention relates to determining biodegradability of certain chelants.
  • Chelants or chelating agents are compounds which form coordinate covalent bonds with a metal ion to form chelates.
  • Chelates are coordination compounds in which a central metal atom is bonded to two or more other atoms in at least one other molecule or ion (called ligand) such that at least one heterocyclic ring is formed with the metal atom as part of each ring.
  • Chelants are used in a variety of applications including food processing, soaps, detergents, cleaning products, personal care products, pharmaceuticals, pulp and paper processing, water treatment, metalworking and metal plating solutions, textile processing solutions, fertilizers, animal feeds, herbicides, rubber and polymer chemistry, photofinishing, and oil field chemistry. Some of these activities result in chelants entering the environment. For instance, agricultural uses or detergent uses may result in measurable quantities of the chelants being in water. It is, therefore, desirable that chelants degrade after use.
  • Biodegradability that is susceptibility to degradation by microbes, is particularly useful because the microbes are generally naturally present in environments into which the chelants may be introduced.
  • Commonly used chelants like EDTA ethylenediamine tetraacetic acid
  • EDTA ethylenediamine tetraacetic acid
  • Tiedje "Microbial Degradation of Ethylenediaminetetraacetate in Soils and Sediments," Applied Microbiology, Aug. 1975, pp. 327-329.
  • Biodegradability is determined according to a standardized test such as ASTM D-2667-89. In that test, a standardized sludge containing organisms from a municipal waste treatment plant is used to biodegrade the chelant in the presence of metal ions representative of those found in the environment including iron. Such a test simulates the environment encountered in a municipal waste treatment plant for screening the inherent biodegradability of non-volatile, water-soluble compounds. Biodegradability according to this test is defined as at least 80 weight percent of a compound biodegraded on a daily basis after an accommodation period of less than or equal to 28 days.
  • onset used to mean the first day that 80 weight percent of the compound is degraded in 24 hours
  • a material is considered borderline biodegradable if onset of biodegradation is between days 29 and 49. Materials are not considered biodegradable if onset of biodegradation takes more than 49 days.
  • the invention is an analytical process for determining biodegradability of compounds of the formula: wherein each of R 2 , R 3 , R 4 , and R 5 is independently hydrogen or an unsubstituted or inertly substituted alkyl, aryl, alkaryl, or aralkyl group and wherein the distance between the carboxyl carbon atoms is designated "Distance A", the distance between carboxyl double bonded oxygen atoms is designated “Distance B", and the distance between carboxyl hydroxy groups "Distance C" comprising: determining, in energetically feasible conformations of a compound having a moiety of Formula 1a, whether at least one of
  • the invention includes a process for determining the biodegradability of compounds having a moiety of the formula: wherein each of R 2 , R 3 , R 4 , and R 5 is independently hydrogen or an unsubstituted or inertly substituted alkyl, aryl, alkaryl, or aralkyl group and wherein, the distance between the carboxyl carbon atoms is designated “Distance A", the distance between carboxyl double bonded oxygen atoms is designated “Distance B", and the distance between carboxyl hydroxy groups "Distance C" comprising:
  • the invention additionally includes a computer system comprising :
  • the invention is the method of using a compound having a moiety of Formula 1a wherein Distance A is from 3.8 to 4.6 Angstroms (A°) (3.8 x 10 -10 to 4.6 x 10 -10 m), Distance B is from 5.1 to 5.9 A° (5.1 x 10 -10 to 5.9 x10 -10 m), and Distance C is from 4.3 to 6.7 A° (4.3 x 10 -10 to 6.7 x 10 -10 m) (hereinafter referred to as a compound of Formula 2 whether in the acid, salt or chelate form) to chelate metal ions by contacting the ions with the acid or salt form of compounds of Formula 2 and subsequently contacting the resultant chelates, residual chenlants or chelants from which the metal is removed with microbes of the type specified for use in ASTM D 2667-89 (both parts) or ISO 5815 (BOD 5 test) or effective enzymes thereof (hereinafter collectively Effective Microbes) under conditions and for a time sufficient for biodegrad
  • the invention is a process of washing comprising contacting an aqueous washing system comprising an organic detergent surfactant selected from the group consisting of anionic detergents, cationic detergents, nonionic detergents, ampholytic detergents, zwitterionic detergents, and mixtures thereof and at least one water-soluble salt of an acid of Formula 2_selected from the group consisting of alkali metal salts, ammonium salts, and alkyl ammonium salts with a material to be washed and subsequently contacting the compound or resultant chelates thereof with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • an organic detergent surfactant selected from the group consisting of anionic detergents, cationic detergents, nonionic detergents, ampholytic detergents, zwitterionic detergents, and mixtures thereof and at least one water-soluble salt of an acid of Formula 2_selected from the group consisting of alkali metal salts, ammonium salts, and alkyl ammonium salts with a
  • the invention includes a cleaning process of contacting with a hard surface, a hard surface cleaning composition comprising at least one acid or salt compound of Formula 2 and subsequently contacting the compound or resultant chelates with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • the invention includes a process of bleaching or bleach-fixing an exposed color photographic material which comprises contacting said material with a bleaching solution or bleach fixing solution containing a bleaching agent comprising a ferric chelate of Formula 2 and subsequently contacting the compound or chelates thereof with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • the invention also includes a process of electroless plating using various metals, especially copper. It includes a process of electroless deposition of copper upon a non-metallic surface receptive to the deposited copper including a step of contacting the non-metallic surface with an aqueous solution comprising a soluble copper salt and an acid or salt compound of Formula 2 and subsequently contacting the compound or resultant chelates with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • Also included is a process of electroless copper plating which comprises immersing a receptive surface to be plated in an alkaline, autocatalytic copper bath comprising water, a water soluble copper salt, and an acid or salt compound of Formula 2 and subsequently contacting the compound and/or resultant chelates thereof with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • Another aspect of the invention includes a process for removing iron oxide deposits from a surface including a step of contacting the deposits with a solution comprising an ammoniated compound of Formula 2 and subsequently contacting the compound or chelates thereof with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • the invention includes a process of removing H 2 S from a fluid comprising contacting said fluid with an aqueous solution at a pH suitable for removing H 2 S wherein said solution contains at least one higher valence polyvalent metal chelate of a compound of Formula 2 and subsequently contacting the compound or chelates thereof with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • Another aspect of the gas conditioning invention includes a process of removing NO x from a fluid comprising contacting the fluid with an aqueous solution of at least one lower valence state polyvalent metal chelate of a compound of Formula 2 and subsequently contacting the compound or chelates thereof with Effective Microbes under conditions and for a time sufficient for biodegradation.
  • the probability of biodegradability or borderline biodegradability is at least 95 percent, more preferably at least 98 percent, most preferably at least 99 percent.
  • the compounds are advantageously biodegradable if other portions of the molecule do not poison microbes involved in biodegradation or Effective Microbes.
  • Determining biodegradability therefore, comprises a step of
  • moiety is used as understood by those skilled in the art to mean part of a molecule, molecular fragment, or molecular structural fragment.
  • R 1 is any molecular structure.
  • R 1 is selected from hydrogen or unsubstituted or inertly substituted alkyl groups, aryl groups, alkaryl groups, or aralkyl groups.
  • R 1 preferably has a structure which renders the compound of Formula 1b soluble and a strong chelant.
  • R 1 is alkyl it preferably contains from 1 to 15 carbon atoms, more preferably from 1 to 10 carbon atoms, most preferably from 1 to 6 carbon atoms.
  • R 1 is aromatic, alkyl aromatic or aromatic alkyl it preferably contains from 5 to 15 atoms, more preferably from 5 to 10 atoms, most preferably from 6 to 8 atoms, in each case preferably carbon or nitrogen atoms, more preferably carbon atoms.
  • R 1 include but are not limited to furan, 2-methyl furan, imidazole, 1-methyl imidazole, 4-methyl imidazole, indole, pyrrole, and 2-methyl pyrrole.
  • inert substitution substitution which does not undesirably interfere with the chelating ability of the compound.
  • exemplary of such inert substitution are hydroxyl, carboxyl, sulfonyl, phosphoryl, amino, imido, and amino groups.
  • Optional inert substitution includes additional iminodiacetic acid groups and derivatives thereof. When there is more than one iminodiacetic acid group, the compound is biodegradable if any one iminodiacetic acid group meets the criteria for biodegradability; therefore, each such group should be tested by the analytical process or in the computer system until at least one meets the criteria.
  • substitution includes hetero atoms (non-carbon atoms) within carbon chains such as in ether groups, pyridine rings.
  • Determining the distance between atoms is within the skill in the art.
  • software with which such determinations are optionally made includes CAChe software commercially available from CAChe Scientific, Inc.; PCMODEL software commercially available from Serena Software; HSC Chemistry for Windows, or PCMODEL software commercially available from AR Software; INSIGHT II, DISCOVER, and LUDI software commercially available from BIOSYM; SYBYL, RECEPTOR, and DISCO software commercially available from Tripos Associates, Inc.; and New Chem-X commercially available from Chemical Design, Inc. Examples of such modeling include those disclosed in U.S.
  • X-ray crystallography data can be used to acertain distances.
  • the crystallography data is preferably input to a programmed computer or microprocessor to determine distances.
  • molecular models can be used to determine inert atomic distances when the models are dimensionally correct. Examples of such modeling include those disclosed in U.S. Patents 4,877,406; 4,906,122; 4,622,014, and 5,030,103. Because of speed and accuracy, determining distances using a programmed computer or microprocessor is preferred.
  • An energetically feasible conformation is a conformation having a heat of formation within 1.5 KCal (6285 Joule (J)) of the heated formation of the lowest, energy conformation.
  • J Joule
  • Ascertaining the lowest conformation in the energetically feasible conformation is within the skill in the art as shown by such references as Reviews in Computational Chemistry II , Lickowitz et al. ed., VCH Publishers, 1991, pp. 1-47 and Hehre et al., Experiments in Computational Organic Chemistry , Wavefunction, Inc., 1993, pp. 47-66. Software is advantageously used in calculating these conformations.
  • the lowest energy conformation and energetically feasible conformations are preferably determined by means known as (a) semiclassical (model), harmonic, or molecular mechanical; (b) semiempirical quantum mechanical; and/or (c) ab initio quantum mechanical methods. These methods are within the skill in the art as shown by Reviews in Computational Chemistry II , Lickowitz et al. ed., VCH Publishers, 1991, pp. 313-315.
  • a compound having a distance A of from 3.8 to 4.6 Angstroms (3.8 x 10 -10 to 4.6 x 10 -10 m), a distance B of from 5.1 to 5.9 Angstroms (5.1 x 10 -10 to 5.9 x10 -10 m) and a distance C from 4.3 to 6.7 Angstroms (4.3 x 10 -10 to 6.7 x 10 -10 m) in their feasible energy conformations can be predicted to be biodegradable or borderline biodegradable that is the onset of biodegradation is within 49 days. Compounds having their feasible conformations outside these ranges are found not to be biodegradable or to have the onset of biodegradation in more than 49 days. Determining whether distances A, B, and C are within these ranges is also preferably done utilizing a programmed digital computer or microprocessor.
  • the process of the invention is preferably carried out using a programmed digital computer or microprocessor in a computer or computerized system. Such a process is diagrammed schematically in Figure I which includes both optional and essential steps.
  • a chemical is advantageously input into the computer system by a means for input of a chemical within the skill in the art.
  • Such means include input via keyboard, via light pen, via a monitor capable of sensing positions of an input device, via any drawing means such as use of a mouse, graphics pad or tablet.
  • Input from a computer system or software either the same computer system or a different one is an alternative means of inputting a chemical and is discussed more fully in the discussion of Figure 2.
  • more than one chemical is input, for example for comparison or convenience.
  • the input chemical is advantageously interpreted into a three dimensional molecular structure and the lowest energy conformation and other low energy conformations are ascertained or determined as represented schematically by Box 2. This determination is within the skill in the art as previously discussed.
  • additional input as represented schematically by Box 3.
  • Box 3 represents such input as rotation of molecular portions (often referred to in the art as "arms") other portions such as is used in determining the lowest energy conformation using such software as Sequential Search or Exhaustive Search options of the CAChe software.
  • X-ray crystallography data is input.
  • the computer system includes a means for determining low or lowest energy conformations without additional input such as is within the state of the art as represented by such software as MOPAC or PCMODEL software.
  • Distance A, Distance B and Distance C are determined in the essential step represented schematically in Box 4. This determination of distance by a computer system is within the skill in the art as previously discussed.
  • Distance A is from 3.8 X10 -10 m to 4.6X10 -10 m
  • Distance B is from 5.1 X10 -10 m to 5.9X10 -10 m
  • Distance C is from 4.3 X10 -10 m to 6.7X10 -10 m. Determining whether numbers representing physical distances are within given ranges is well suited to computer systems and is well within the skill in the art. Determining whether the distances are within the ranges is critical to the practice of the invention. As indicated by Figure 1, it is not, however, necessary that all the distances be compared with their ranges if one is found to be outside its range.
  • the computer system preferably has a means for verifying that the conformation measured is, in fact, the lowest energy conformation or an energetically feasible one as schematically represented by optional Box 8. This step is optional because the more readily biodegradable molecules having a moiety of Formula 1a are identified by their lowest energy conformations having the specified dimensions.
  • Box 9 schematically represents a determination of whether there are additional energetically feasible conformations. If there are, the steps represented by Boxes 4, 5, 6 and 7 are repeated. If there are not other energetically feasible conformations, then the molecule whose energetically feasible conformations have not met the criteria represented in Boxes 5, 6 and 7 are determined not to be biodegradable within 49 days.
  • Figure 2 illustrates an advantageous variation on the system represented in Figure 1. More than one chemical structure is considered.
  • the steps and means represented by Boxes 1-11 are as described for Figure 1 except that the advantageous output function of Boxes 10 and 11 is preferably replaced by the output represented by Box 14.
  • the system checks for whether to proceed as represented by Box 12.
  • Box 12 represents a means within the skill in the art, for instance a counter, a check of how many groups have been added to what positions, a check of how many variations have been not biodegradable (for example a percentage or a number of consecutive non-biodegradable compounds), a check of the molecular weight or number or ratio of specified atoms, a counter of the time the system has been running or a combination of these.
  • Optional Box 13 which is executed if the test of Box 12 succeeds, schematically represents a change in the molecular structure from that originally input in Box 1.
  • a change is within the skill in the art.
  • methylene groups, aromatic groups and/or preselected substitutents are successively added at predetermined positions on a molecule.
  • a predetermined sequence of R groups (used generically for R 1 , R 2 , R 3 , R 4 , and R 5 ) are considered for the structures of Formula Ib.
  • a change is considered preselected if it is a change in a programmed sequence of changes including, but not limited to, a sequence of molecular structures in a input file or other input sequence.
  • Compounds having a moiety of Formula Ia having these intraatomic dimensions, their salts and chelates are referred to herein as compounds of Formula 2.
  • Examples of compounds of Formula 2 include
  • Preparation of compounds of Formula 2 is within the skill in the art, for instance, by processes described by F. C. Bersworth in U.S. Patents 2,387,735 and 2,407,645. These patents detail the reaction of cyanide ion, formaldehyde, and various amines in a basic medium to produce various carboxymethylated amines of the type used in this invention.
  • a second process for the preparation of compounds of Formula 2 is described by H. Schlapfer and J. Bindler in U. S. Patent 2,709,179 where a haloacetic acid is reacted with an amine to prepare a carboxymethylated amine which may be one of the compounds described as Formula 2.
  • a third process for the preparation of compounds of Formula 2 is described by Y.
  • Urano and Y. Kadano in U. S. Patent 5,220,055 which details the oxidation of various aminoalcohols in the presence of an alkali metal hydroxide to produce corresponding carboxymethylated amines which are potential compounds of Formula 2. Variations on these methods are within the skill in the art.
  • Compounds of Formula 2 are effective as chelants especially for metals such as iron and copper. Effectiveness as a chelant is conveniently measured by titrating the chelant with copper in the presence of an indicator dye, using as an endpoint detector a photosensitive electrode.
  • the stability constant is conveniently calculated by comparing potentiometric pH measurement of the chelant in the absence of and in the presence of known concentrations of metal ion as described in Determination and Use of Stability Constants by Martell and Motekaitis, VCH Publishers, 1985, pp. 14 and 21-27. Various methods may be employed to determine stability constants.
  • Biodegradable chelants are useful, for instance, in food products vulnerable to metal-catalyzed spoilage or discoloration; in cleaning and laundering products for removing metal ions, for example from hard water, that may reduce the effectiveness, appearance, stability, rinsibility, bleaching effectiveness, germicidal effectiveness or other property of the cleaning agents; in personal care products like creams, lotions, deodorants and ointments to avoid metal-catalyzed oxidation and rancidity, turbidity, reduced shelf-life; in pulp and paper processing to enhance or maintain bleaching effectiveness; in pipes, vessels, heat exchangers, evaporators, filters to avoid or remove scaling, in pharmaceuticals; in metal working; in textile preparation, desizing, scouring, bleaching, dyeing; in agriculture as in chelated micronutrients or herbicides; in polymerization or stabilization of polymers; in photography, for example in developers or bleaches; in the oil field such as for drilling, production, recovery, hydrogen sulfide abatement.
  • metals include alkaline earth metals and heavy metals including Fe, Cu, Mn, Zn, Pb, Hg, Ni, Cr, Co, W, Sn, Va, Ti, Ta, Pt, Pd, Zr, Mo, Ca, Mg and Sr.
  • biodegradable chelants also includes bleaching agent stabilization, for example for sodium perborate, in detergents and in the bleaching of textiles, pulp or paper stock.
  • bleaching agent stabilization for example for sodium perborate
  • Traces of heavy metals, such as iron, copper and manganese are present in washing compositions themselves, in water and in textile or pulp material, and they catalyze the decomposition of the sodium perborate or other bleaches.
  • the chelants according to the invention bind these metal ions and prevent the undesirable decomposition of the bleaching system during storage and in the wash liquor. This enhances the efficiency of the bleaching system and reduces fiber damage.
  • Such processes are within the skill in the art such as represented by U. S. Patents 4,923,941; 4,792,611; 4,822,886, and 4,655,954.
  • biodegradable chelants can be used as preservatives advantageously in an amount from 0.05 to 15 percent by weight, based on the total weight of the formulation.
  • Such processes are within the skill in the art such as represented by U. S. Patent 5,045,580.
  • biodegradable chelants prevent, for example, metal catalyzed oxidative decompositions.
  • the chelants can be used in industrial processes whenever precipitates of Ca, Mg and other heavy metal and alkaline earth salts are a nuisance and are to be prevented. They are used, for example, for preventing scale deposits and encrustations in kettles, pipelines, spray nozzles or generally on smooth surfaces. Such processes are within the skill in the art such as represented by U. S. Patents 4,683,008; 4,606,850; 4,357,254; 4,496,470; 3,460,989, and 4,005,506.
  • the chelants are suitably used for preparing for example the redox catalysts used therein. They additionally prevent the precipitation of such compounds as iron hydroxide in an alkaline polymerization medium.
  • the chelants are suitably used in developer/fixing baths made up with hard water to alleviate precipitations that lead to fogging on films and photographs and alleviate deposits in the tanks.
  • Iron(III)-complexes of the biodegradable chelants solutions are advantageously used in bleaching and/or bleach fixing baths to bleach silver off exposed color photographic materials.
  • Such processes are within the skill in the art such as represented by U. S. Patents 3,893,858; 4,294,914; 4,707,434; and 4,933,266.
  • the chelants are suitably used for removing heavy metal traces during the manufacture and dyeing of natural and synthetic fibers, thereby preventing many problems, such as dirt spots and stripes on the textile material, loss of luster, poor wettability, unlevelness and off-shade dyeings.
  • Such processes are within the skill in the art such as represented by U. S. Patents 4,619,663; 3,539,445, and 4,339,236.
  • the chelants are suitably used for eliminating heavy metal/iron ions. Iron deposits on paper lead to hot spots where oxidative, catalytic decomposition of the cellulose starts.
  • Such processes are within the skill in the art such as represented by U. S. Patents 4,732,650; 4,734,161; 4,938,842; 5,143,580; 5,143,581, and 3,830,690.
  • Exemplary of various other uses are applications in pharmaceuticals, cosmetics and foodstuffs where metal catalyzed oxidation of olefinic double bonds and hence rancidification of goods is prevented.
  • the chelates are also useful as catalysts for organic syntheses (for example air oxidation of paraffins, hydroformylation of olefins to alcohols).
  • the chelants for alkaline earth metal and heavy metal ions according to the invention are used as complexing agents in general and specifically in detergents and also rinse and wash assistants, in particular as complexing agents for heavy metal and/or alkaline earth metal ions, as bleaching agent stabilizers and as builders.
  • Such processes are within the skill in the art such as represented by U. S. Patents 4,997,587; 4,983,315; 4,906,397; 4,698,181; 4,436,637; 4,439,355, and 4,207,198.
  • Chelants of the invention are also useful in surfactant-free cleaning compositions including built cleaning compositions suitable for hard-surface cleaning, such as certain automatic dishwashing agents and kitchen or bathroom cleaners.
  • cleaning compositions generally comprise from 1 percent to 99.95 percent, preferably 90 percent to 99 weight percent, of a conventional builder and at least 0.5 weight percent, typically 0.1 to 5 weight percent chelant.
  • the hard surface cleaners preferably include at least one organic solvent with the chelant and, more preferably also contain at least one builder and/or surfactant.
  • builders which are primarily polyphosphates or nitrogenous chelants like NTA with terpenes, benzyl alcohol or butyl carbinol are discussed in European Patent Applications 40,882; 80,749 and 126,545.
  • glycol ether derivatives as solvents are discussed in European Patent Application 105,863 and U.S. Patent 3,591,510 which patents are incorporated herein by reference in their entireties. More recently, it was noted that solvents preferably have a boiling point of at least 90°C. (See European Patent Applications 317,542 and 513,948 and U.S. Patent 5,202,050.
  • Use of solvents of at least 90°C results in improved soil-release benefits from the chelate-solvent composition, especially in the removal of calcium soap-soil from surfaces such as bathtub surfaces.
  • Electroless plating is the controlled autocatalytic deposition of a continuous film of metal without the assistance of an external supply of electrons such as is described in U.S. Patents 3,119,709 (Atkinson) and 3,257,215 (Schneble at al.).
  • Non-metallic surfaces are pretreated by means within the skill in the art to make them receptive or autocatalytic for deposition. All or selected portions of a surface are suitably pretreated.
  • Complexing agents are used to chelate a metal being deposited and prevent the metal from being precipitated from solution (that is as the hydroxide). Chelating a metal renders the metal available to the reducing agent which converts the metal ions to metallic form.
  • Such electroless plating is especially useful in the electronics industry, especially for printed circuits.
  • Metal chelates are important in agriculture because they supply micronutrients (trace metals such as iron, zinc, manganese, and copper) which are vital in the metabolism of both plants and animals. Plant problems previously ascribed to disease and drought are now recognized as possible symptoms of micronutrient deficiencies.
  • these metal chelates are more readily utilized by the plant than are the inorganic forms of the metals. This is especially true in highly competitive ionic systems. As a result, the micronutrients that are chelated to the biodegradable chelants are more efficient than when compared to the inorganic sources.
  • the chelates of iron, manganese, copper, and zinc with the biodegradable chelants are particularly preferred. Biodegradable chelants have less residence time in soil. Such processes are within the skill in the art such as represented by U. S. Patents 4,322,361; 4,312,815, and 4,364,871.
  • biodegradable chelants include gas washing, conditioning or scrubbing (of for example flue, geothermal, sour, synthesis, process, fuel, or hydrocarbon gas) to remove at least one acidic gas, preferably the removal of NO x from flue gases, H 2 S oxidation and metal extraction.
  • gas washing, conditioning or scrubbing of for example flue, geothermal, sour, synthesis, process, fuel, or hydrocarbon gas
  • Polyvalent metal chelates of the biodegradable chelants are particularly useful in removing H 2 S from a fluid, particularly a gas, containing H 2 S, by (directly or indirectly) contacting the fluid with at least one chelate of at least one, preferably one polyvalent metal in a higher valence state such that sulfur is formed along with the chelate of the metal in a lower valence state.
  • the chelate of any oxidizing polyvalent metal capable of being reduced by reaction with H 2 S or hydrosulfide and/or sulfide ions and, preferably which can be regenerated by oxidation, is suitable.
  • the chelates are water soluble.
  • Exemplary metals include lead, mercury, nickel, chromium, cobalt, tungsten, tin, vanadium, titanium, tantalum, platinum, palladium, zirconium, molybdenum, preferably iron, copper, or manganese, most preferably iron.
  • the biodegradable chelants are suitably used in any process of removal of H 2 S within the skill in the art such as those exemplified by United States Patents 4,421,733; 4,614,644; 4,629,608; 4,683,076; 4,696,802; 4,774,071; 4,816,238; and 4,830,838.
  • the polyvalent metal chelates are readily formed in aqueous solution by reaction of an appropriate salt, oxide or hydroxide of the polyvalent metal and the chelating agent in the acid form or an alkali metal or ammonium salt thereof.
  • the biodegradable chelants are used in removal of nitrogen oxides, preferably nitric oxide (NO), from fluids containing them.
  • nitrogen oxides (NO X ) and SO 2 can be removed from flue gas streams by absorbing the SO 2 using an absorbent or reactant therefor, particularly an amine based absorbent such as a nitrogen-containing heterocyclic compound preferably having at least one carbonyl group such as a piperazinone; piperidinone, piperidine, piperazine or triazine having a carbonyl group; hydantoin; cyclic urea, oxazolidone of morpholinone in conjunction with a chelate of a polyvalent metal.
  • an absorbent or reactant therefor particularly an amine based absorbent such as a nitrogen-containing heterocyclic compound preferably having at least one carbonyl group such as a piperazinone; piperidinone, piperidine, piperazine or triazine having a carbonyl group; hydantoin
  • Representative metal ions are chromium, cobalt, copper, iron, lead, manganese, mercury, molybdenum, nickel, palladium, platinum, tin, titanium, tungsten, and vanadium; preferably iron, copper, and/or nickel all preferably with a valence of +2, the more preferably iron, most preferably iron in the ferrous state.
  • Such chelates are conveniently prepared by admixing a water soluble salt of the metal, such as a sulfate or acetate with a water soluble form of the chelating agent, for example a salt, advantageously in water.
  • the chelates are useful in any process within the skill in the art such as those disclosed in United States Patents 4,732,744 to Chang et al.; 4,612,175 to Harkness et al.; 4,708,854 to Grinstead; 4,615,780 to Walker; 4,126,529 to DeBerry; 4,820,391 to Walker; and 4,957,716 to Cichanowicz et al.
  • SO 2 absorbent When an SO 2 absorbent is used, it is preferably regenerated, more preferably thermally regenerated, and preferably recycled.
  • the concentration of NO X in the fluid (directly or indirectly) contacting the chelate is preferably from 1 ppm to 15,000 ppm by volume such as is found, for instance, in flue gases from burning for example coal.
  • biodegradability of compounds of Formula 2 renders these processes novel when combined with a biodegradation step.
  • a biodegradation step involves contacting compounds of Formula 2 with microbes such as are specified for ASTM 2667-89, ISO 5815 (BOD 5 test) or effective enzymes thereof under conditions and for a time sufficient to result in degradation, preferably of at least 80 weight percent of the compounds of Formula 2.
  • the time for accommodation is preferably less than or equal to 49 days more preferably less than or equal to 35 days, most preferably less than or equal to 28 days.
  • the compounds of Formula 2 advantageously biodegrade within at least 24 hours, more preferably at least 12 hours, most preferably at least 8 hours.
  • Preferred conditions include contacting compounds of Formula 2, preferably in concentrations below 1 millimolar, with environmentally obtained microbes in an aerated, aqueous solution with an exogenous supply of nutrients for the microbes, more preferably contacting compounds of Formula 2 in concentrations of below 0.1 millimolar with microbes obtained from the activated sludge of a municipal waste treatment plant in an aerated, aqueous solution with intermittent exogenous supply of a portion of the protein and carbohydrate nutrient requirements of the microbes such as is within the skill in the art, for instance as discussed in ASTM 2667-89.
  • the microbes are advantageously environmentally obtained bacteria, preferably environmentally obtained bacteria from aqueous solutions more preferably bacteria obtained from municipal waste treatment plants as activated sludge.
  • microbes obtained from soil, water, sewage, public waste water treatment plants such as is discussed in ASTM 2667-89, especially for the presumptive test. While environmentally obtained microbes are preferred, those skilled in the art will recognize that other microbes, including commercially obtained and bioengineered microbes are suitably used as are enzymes from or acting similarly to the enzymes of any of the microbes. Thus any microbe, enzyme or the like which degrades the compound of Formula 2 is suitably used.
  • CAChe software was used to calculate and display molecular orbitals, charge distribution, the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) for the lowest energy conformations.
  • HOMO highest occupied molecular orbital
  • LUMO lowest unoccupied molecular orbital
  • the measured distances in the lowest energy conformations are listed in Table 2. For each compound, the distances which fall outside the preferred range are underlined and given in bold print.
  • Four extra conformations are included in Table 2 - one extra conformation each for compound I, compound X, compound XI, and compound XII. These conformations are the next higher energy conformation for each of the molecules. The energy difference between these conformations and the lowest energy conformations is small enough to allow significant population of the higher energy conformations at room temperature.
  • the populations of these second conformations are calculated from the Boltzmann distribution to be 30 percent, 89 percent, 32 percent, and 28 percent, respectively, of the populations of the lowest energy conformations of the four compounds.
  • biodegradable and borderline compounds have an energetically favorable conformation which has all three distances within the preferred limits.
  • All of the non-biodegradable compounds have at least one distance that is outside the range of the preferred limits for the distances. None of the non-biodegradable compounds has an energetically feasible conformation with all three distances within the preferred limits.
  • Table 1 lists the names of the compounds and the number of days until onset of biodegradation as measured by the procedure of ASTM 2667-89, the Semicontinuous Activated Sludge test.

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EP99115513A 1994-07-27 1995-07-14 Bestimmung der Biodegradabilität von Iminodiessigsäurederivateb, abbaubare Chelatbildner sowie deren Verwendung und Zusammensetzungen damit Withdrawn EP0971230A1 (de)

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US6420329B1 (en) * 1995-10-26 2002-07-16 S. C. Johnson & Son, Inc. Cleaning compositions
DE19726427A1 (de) * 1997-06-23 1998-12-24 Boehringer Mannheim Gmbh Pyrimidin-2,4,6-trion-Derivate, Verfahren zu deren Herstellung und diese Verbindungen enthaltende Arzneimittel
DE19852972A1 (de) * 1998-11-17 2000-05-18 Henkel Kgaa Färbemittel mit Übergangsmetallkomplexen
US6334099B1 (en) * 1999-05-25 2001-12-25 Digital Gene Technologies, Inc. Methods for normalization of experimental data
EP2542248A4 (de) 2010-03-02 2013-04-17 Univ Kansas Polyamin-dihydroxybenzoesäurekonjugat-hydrogele als eisenchelatbildner

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